CN1070334A

CN1070334A - The Hairspray compositions of fluorine-containing surfactant

Info

Publication number: CN1070334A
Application number: CN92110878.8A
Authority: CN
Inventors: M·M·佩夫利
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1991-08-19
Filing date: 1992-08-19
Publication date: 1993-03-31
Also published as: GR3020298T3; FI940770A0; ES2088590T3; CZ35194A3; SK19394A3; PT100790A; NO940537L; EP0600013A1; NZ243995A; JPH06509808A; MX9204801A; BR9206386A; FI940770A; AU671598B2; CA2115155A1; MY137278A; DK0600013T3; WO1993003705A1; DE69211699D1; EP0600013B1

Abstract

The present invention relates to be used for the Hairspray compositions of spray application on hair, it contains the ion fluorine surfactant of the 0.01%-that has an appointment about 2%, the ion exchange resin of about 0.1%-about 15% and a kind of liquid excipient.

The present invention also relates to be used for the Hairspray compositions of spray application on hair, it contains the ion fluorine surfactant of the 0.01%-that has an appointment about 2%, ionic macromolecular resin and a kind of liquid excipient of haircuting of silicone that contain of about 0.1%-15%.

The invention still further relates to Hairspray compositions, it contains the ion fluorine surfactant of the 0.01%-that has an appointment about 2%, ionic macromolecular resin and a kind of liquid excipient of haircuting of silicone that contain of about 0.1%-about 15%.

Description

The Hairspray compositions of fluorine-containing surfactant

The present invention is application on August 19th, now resigned, and the part of its application number No.07/747163 continues.

The present invention relates to hair is kept in-situ Hairspray compositions,, can make things convenient for and disperse equably by aerosol or spraying disperser.

People's universal demand makes hair fully remain on specific hair style.The most frequently used for this reason method is to use a kind of compositions, and with the hair moistening, washing is or/and hair care or dry then, and Hair styling is finished.These compositionss provide the advantage of temporarily haircuting, and will lose when water or shampoo washing.Being used to provide the haircut composition material of advantage generally is resin, and with mousse, gel, lotion or spray form are used.

Many people require to use Hairspray compositions, so that hair style keeps or keeps high-levelly.General hair jelly is by using resin, as the AMPHOMER that is provided by National Starch and Chemical Company

With the GANTREZ SP 225 that provides by GAF

And reach the maintenance hair style.The weight average molecular weight of these resins is generally about 40000 to about 150000.When this resin being incorporated in pump or the aerosol hair jelly, can provide persistency and good sprayability.Usually, use Hairspray compositions with increase hair style retention time, but the sense of touch of hair becomes harder and denser, this is unwelcome.Therefore requirement can provide a kind of and can keep hair style and have the good hair jelly product of hair sense of touch concurrently.

Have now found that it is useful using the resin of higher weight average molecular weight,, and reduced and reach that good hair style keeps institute's necessity and the resin demand that mixes because these resins can provide the persistency of general desired increase hair style.

Unfortunately, using this higher molecular weight resin, have weight average molecular weight greater than about 300000 resin as those, is the comparison difficulty in aerosol and spraying glue preparation.This preparation has relatively poor pulverability, and for example, the feature of the spraying style that they had is moistening droplet-like center, or the spray feature that it had is the liquid stream shape, rather than the hair jelly granule of fine mist.Because the difficulty in spraying higher molecular weight resin causes actual worry, as adhering to and poor stability in use, and the hair sense of touch and the retentivity that cause difference usually, then the purpose of this invention is to provide a kind of Hairspray compositions, it has the advantage that high molecular weight resin has, and does not have because of the difficulty of this compositions of the spraying performance with character or the passiveness that state was caused.

Usually hair jelly also is to use a large amount of monoalcohol solvents, prepares as the water of ethanol and isopropyl alcohol and relatively small amount, because there is water can influence spray effect.But wish to prepare Hairspray compositions now especially with the volatile organic solvent of reduction amount such as ethanol and isopropyl alcohol.A kind of method is the water yield that increases in the preparation.Do like this, very strong requirement will be arranged, so that the product of preparation to be provided again, it can overcome usually with in the hair jelly product and adds the relevant problem of water.Particularly, the water of higher amount can make increase drying time, and the sense of touch of hair is had bad influence.

It is difficult especially that the resin of haircuting that will contain silicone macromole (macromer) is formulated in the Haircare composition.Use contains the sense that the silicone macromolecule polyalcohol can make Hairspray compositions have a typing (or haircuting) simultaneously and improve, as, compared flexibility with a common styling polymer.This silicone macromolecule polyalcohol that contains can use by various scope molecular weight.The lower molecular weight polymer as by about 50000～300000, has the characteristic of poor atomization quality than the common polymer of haircuting.And higher molecular weight is to be difficult to prepare in the compositions that good spraying character is into arranged.It is much higher that the molecular resin amount that is used for this type of composition is compared with the resin of the most commercial hair jelly, has therefore increased the weight of the atomization quality problem.

Fluorizated surfactant, this paper is called fluorine surfactant, is known shampoo and the flushing compositions of being used for.The people's such as Goebel of issue on January 15th, 1980 United States Patent (USP) 4183367 discloses to use in shampoo and flushing compositions fluoridizes cationic and amphoteric surfactant, impels dry quickly washing hair with the water yield of staying by reduction in the hair.The people's such as Callingham that JIUYUE in 1981 was published on the 30th British patent 1599414 discloses to be used anionicly, amphoteric in shampoo composite, and non-ionic or cationic fluorine surfactant is to obtain the lipotropism effect.

Disclose at the people's such as Cella of the people's such as Cella of on November 23rd, 1976 issue United States Patent (USP) 3993745 and issue on November 23rd, 1976 United States Patent (USP) 3993744 fluorine surfactant has been used for containing generally haircut resin and the general hair jelly that contains low amounts of water.Disclose with these compositions-treated hairs, the mistake that delays sebum effectively distributes.

Find now, in the hair jelly solution that contains ionic resin and relative high-load water, add ionic fluorine surfactant and can make hair jelly have excellent characteristic.This compositions can further be improved the sense of touch of hair, and with usually, the compositions of low water content is not relatively having aspect the hair style or is seldom reducing keeping.Discovery is sent out fluorine surfactant molding resin and is combined with containing the silicone macromole, in general, can have good hair jelly performance, no matter is low or special in high water content Hairspray compositions.Contain extra high molecular weight to contain haircut use fluorine surfactant in the hair jelly of resin (according to appointment 300000 and higher) of ion be the high molecular weight resin that is particularly conducive in those spray composites that are difficult to be formulated into good pulverability especially.

Can confirm that by the description below of the present invention these advantages and other advantage are tangible.

The present invention relates to be used in the Hairspray compositions of on hair, spraying, comprise about ion fluorine surfactant of 0.01%～about 2%, about 0.1%～about 15% ion exchange resin and a kind of liquid excipient, wherein the feature of Hairspray compositions is to use and contains the macromolecular resin and/or contain a large amount of relatively water of haircuting of silicone, and is promptly moisture and contain higher water gaging.（waterand higher）

The present invention also relates to be used in the Hairspray compositions of spraying on the hair, comprise about ion fluorine surfactant of 0.01%～about 2%, about 0.1%～about 15% contains macromolecular resin and a kind of liquid excipient of haircuting of ion silicone.

The invention still further relates to a kind of Hairspray compositions, it contains the 0.01%～about 2% ion fluorine surfactant of having an appointment, about 0.1%～15% contains macromolecular molding resin of ion silicone, and a kind of liquid excipient, and the resin of wherein haircuting has the weight average molecular weight at least about 300000.

Unless refer else, whole percentage rate herein are the weight by hair jelly.

Below used in the present invention key component and optional component all are described in.

Fluorine surfactant

Composition of the present invention contains a kind of ion fluorine surfactant to be formed as main.The ion fluorine surfactant can be selected from cation fluorine surfactant, anionic fluorinated surfactant, both sexes fluorine surfactant, zwitterionic fluorine surfactant and composition thereof.

Fluorine surfactant is basically in order to obtain good spraying ability.Can think that this advantage is to provide because of the interaction that makes the Hairspray compositions viscosity degradation.

Fluorine surfactant is a kind of surface-active reagent.Generally, fluorine surfactant is a kind of a kind of molecule that contains hydrophilic segment and contain the hydrophobic part of fluorohydrocarbon.Useful fluorine surfactant can be linearity or branched alkyl in this compositions, the fluorohydrocarbon of alkenyl or alkylaryl, and the chain length that it has is about 3～18 carbon atoms, and is all or part of fluoridizing.Hydrophilic segment can be a sulfate, phosphate, phosphonate, sulfonate, amine, amine salt, quaternary ammonium, carboxylate and any its conjugate.Between hydrophilic and hydrophobic part also can be the bridging part, as a kind of acylamino-alkylidene.

The fluorine surfactant that is used for the present composition is any fluorinated surfactant with ionic nature.This available fluorine surfactant can be any fluorinated hydrocarbons surfactant with required feature.

A class ion fluorine surfactant that is used for the present composition is following surface chemistry formula to be the fluoridized chemical compound of representative;

Wherein Z is the water solubilization radical of organic or inorganic character, and x is generally 2～17, preferably 7～11 integer, and y is 0～4 integer, and described chemical compound can be cationic, anionic, amphoteric or zwitterionic, this is decided by the group that Z comprises or the character of group group.The Z group can be maybe can contain sulfate, sulfonate, carboxylate, amine salt, quaternary ammonium, phosphate, phosphonate and conjugate thereof.Fluoridized chemical compound is known in the prior art.These chemical compounds are described in the people's such as Cella that announced on November 27th, 1979 United States Patent (USP) 4176176, the people's such as Cella that the people's such as Cella that on November 23rd, 1976 announced United States Patent (USP) 3993745 and on November 23rd, 1976 announce United States Patent (USP) 3993744, these all list in for referencial use herein.

Suitable anionic fluorinated surfactant can have the carboxylate of comprising, sulfate, sulfonate, the anionicsite of phosphonate and phosphate or its any conjugate.Therefore counter ion counterionsl gegenions can comprise sodium, ammonium, magnesium, potassium, triethanolamine, diethanolamine, and similar portions.Suitable cation fluorine surfactant can have the cationic moiety that comprises quaternary ammonium compound, and its counter ion counterionsl gegenions can be chloride or any other halogenide, metilsulfate, ethylsulfate, phosphate, acetate and other similar portions.Suitable cation fluorine surfactant also can have comprise acid primary, the second month in a season and tertiary ammonium salt, example hydrochloric acid, lactic acid, phosphoric acid, sulphuric acid and the similar cationic moiety of acid.The both sexes fluorine surfactant contains-carboxylate and-amine groups.The amphion fluorine surfactant contains just like carboxylate, sulfate, and the anionicsite of sulfonate and phosphate group or other similar group, and for example, the cationic moiety of quaternary ammonium or amine salt.Should be noted that term " amphoteric " and " zwitterionic " chemical supply company can be used alternatingly, and the classification of the fluorine surfactant of this paper can be different from the classification that supply company gives.

Used preferred cation fluorine surfactant comprises having various anionic counter-ions in this compositions, comprises iodide, chloride, metilsulfate, phosphate and nitrate, the fluorinated alkyl quaternary ammonium salt of the anionic counter-ion of iodide preferably, and those are according to chemical formula R _fCH ₂CH ₂SCH ₂CH ₂N ⁺(CH ₃) ₃[CH ₃SO ₄] ^-, R wherein _f=F(CF ₂CF ₂) ₃_ ₈Fluorine surfactant such as the Zonyl FSC of Dupont supply ^RPreferred fluorinated alkyl quaternary ammonium iodide is provided by 3M, with trade name Fluorad FC-135 Sell.

Used preferred anionic surfactants fluorine surfactant is single and two perfluoroalkyl phosphate in the present composition, the Zonyl FSP that provides as Dupont

, and according to general formula (R _fCH ₂CH ₂O) (ONH P(O) ₄) ₂(R _fCH ₂CH ₂O) ₂P(O) (ONH ₄), R wherein _f=F(CF ₂CF ₂) ₃_ ₈Single and two fluoroalkyl phosphates have various cation counterbalancing ions, as ammonium, sodium, potassium, triethanolamine and diethanolamine salt, preferably with the ammonium salt of nonfluorinated quaternary amine (guats) ligand compound, aliphatic quaternary ammonium metilsulfate preferably is as the Zonyl FSJ that Dupont provided

; Perfluoroalkyl sulfonic acid, it has various cation counterbalancing ions such as ammonium, sodium, potassium, triethanolamine and diethanolamine salt, ammonium salt preferably is as the Zonyl TBS that Dupont provided

And according to chemical formula R _fCH ₂CH ₂SO ₃X, wherein R _f=F(CH ₂CH ₂) ₃_ ₈, and X=H and NH ₄; Telomer phosphate has various counter cations, as ammonium, and sodium, potassium, triethanolamine and diethanolamine salt, diethanolamine salt preferably is as the Zonyl RP that Dupont provided The perfluoroalkyl sulfanilic acid is as the Fluorad FC-99 that 3M provided

; The perfluoroalkyl ichthyodin, the Fluorad FC-93 that provides as 3M

, Fluorad FC-120

And L-12402

; The perfluoroalkyl potassium sulfonate, the Fluorad FC-95 that provides as 3M

With Fluorad FC-98

; Fluorinated alkyl carboxylic acid potassium is as Fluorad FC-129

And provide by 3M; The perfluoroalkyl carboxylic acid ammonium, the Fluorad FC-143 that provides as 3M

, these fluorine surfactants are according to general formula R _fCH ₂CH ₂SCH ₂CH ₂CO ₂Li, wherein Rf=F(CF ₂CF ₂) _3-8, as the Zonyl FSA that provides by Dupont

The preferred anionic surfactants fluorine surfactant is blended single and two perfluoroalkyl phosphate, ammonium salt; Blended single and two fluorinated alkyl phosphate, ammonium salt is with the coordination compound of aliphatic season metilsulfate; Perfluoro alkyl sulfonic acid, amine salt; Blended telomer phosphate diethanolamine salt; The perfluoroalkyl sulfanilic acid; The perfluoroalkyl ichthyodin; The perfluoroalkyl potassium sulfonate; Fluorizated hydrocarbon carboxylic acids potassium; The perfluoroalkyl ichthyodin; With the perfluoroalkyl carboxylic acid ammonium.

The preferred both sexes fluorine surfactant that is used for this compositions is that fluorinated alkyl is amphoteric, the Fluorad FC-100 that provides as 3M

; And the both sexes fluorine surfactant L-12231 of the experiment that provides of 3M.

The preferred zwitterionic fluorine surfactant that is used for this compositions is according to chemical formula R _fCH ₂CH(OCOCH ₃) CH ₂N ⁺(CH ₃) ₂CH ₂CO - ₂Rf=F(CF wherein ₂CF ₂) _3-8Those fluorine surfactants such as the Zonyl FSK that provides of Dupont

Above-mentioned fluorine surfactant can use separately or be used in combination in Hairspray compositions of the present invention.

In Hairspray compositions of the present invention, preferably can use amphoteric or zwitterionic and anionic fluorinated surfactant and anionic and mixture cation fluorine surfactant.The preferred amphion and the anion mixture that use are the Zonyl FSK that is provided by Dupont

With the Fluorad FC-100 that provides by 3M

Mixture and the Zonyl FSK that provides of Dupont

The Zonyl TBS that provides with Dupont

Mixture.The mixture of preferred anionic surfactants and cation fluorine surfactant is that 3M is with Fluorad FC-95

The perfluoroalkyl potassium sulfonate that provides and by 3M with Fluorad FC-135 The mixture of the fluorinated alkyl quaternary ammonium iodide that provides.

Combining with a kind of diffluent fluorine surfactant by hanging down molten fluorine surfactant, is favourable with the dissolubility that improves low molten fluorine surfactant.For example with Zonyl FSK

With a kind of diffluent Fluorad FC-100

Be mixed with mutually and help low molten Zonyl FSK

Dissolubility.

A kind of ion fluorine surfactant that is used for Hairspray compositions of the present invention, preferably be selected from cation fluorine surfactant, anionic fluorinated surfactant, the both sexes fluorine surfactant, zwitterionic fluorine surfactant and composition thereof, its consumption is about 0.01%～about 2%, preferably about 0.01%～about 1.5%.Most preferred consumption is about 0.02～about 1%.

Resin

Being used for sending out the ion exchange resin of finalizing the design is a Main Ingredients and Appearance of the present invention.Resin mainly is to be used to keep hair style.

" ion exchange resin " used herein is meant any ionomer or the polymer that the benefit of haircuting can be provided, and be natural or synthetic.Such polymer is known in the prior art.In general, the amount of a used styling polymer is at least about 0.1%(weight of compositions).Usually, it can be about amount of 0.1%～about 15%, preferably about 0.5%～about 8%, and better be about 1%～about 5%.

The weight average molecular weight that polymer had of this compositions can be to be used to provide any molecular weight of benefit of haircuting.Usually, weight average molecular weight is at least about 30000, generally at least about 50000 preferably at least about 60000.In particular cases of the present invention, use very high mean molecule quantity resin, it is at least about 300000.This can not think has any critical upper limit to molecular weight, as long as resulting composition must be sprayable by means of fluorine surfactant.In general, molecular weight can be less than 10000000, preferably is less than 5000000, is more preferably to be less than about 3000000.

This paper contains the macromolecular resin of haircuting of silicone, and preferred weight average molecular weight is at least about 50000, preferred at least about 70000,100000 in addition preferably by about 100000～about 1000000, best is about 125000～about 200000.

This paper resin also is an ionic nature.Here used " ion exchange resin " " ionomer " or term " ionic nature " are about polymer or monomer, and this polymer comprises that the meaning is meant anionic, cationic, amphoteric, zwitterionic or can be present in polymer in the liquid excipient of sending out Hairstyling composition with the disassociation form.

Any kind ionomer, if can be dissolved or dispersed in liquid-carrier can both be used for the present invention.In the prior art, such various polymer is known.

Ionomer of the present invention can be homopolymer, copolymer, trimer etc.The present invention is used, term " polymer " " will comprise whole such polymeric materials.

As main aspect, resin of the present invention must comprise the monomer of ion characteristic.For ease of describing polymer of the present invention, the monomeric unit in polymer can be those their deutero-monomers thus.Ion monomer can be by polymerisable ion initial monomers or by polymerisable, and correctability is the non-ionic monomer of ion characteristic after the polymerization.Ion monomer of the present invention comprises monomeric salt, the bronsted lowry acids and bases bronsted lowry that the present invention exemplifies.

The example of anionic monomer comprises:

(ⅰ) undersaturated carboxylic acid monomer is as acrylic acid, methacrylic acid, maleic acid, maleic acid half ester, itaconic acid, Fumaric acid and butenoic acid;

(ⅱ) half ester of unsaturated polyprotic acid anhydride, as succinic anhydrides, the acrylate and/or the methacrylate of phthalic acid etc. and a hydroxyl group, as hydroxy ethyl methacrylate, hydroxyethyl meth acrylate, reaction such as hydroxypropyl acrylate;

(ⅲ) have sulfonic monomer, as styrene sulfonic acid, sulfur ethyl propylene acid esters and methacrylate etc.;

(ⅳ) has the monomer of phosphate group, for example phosphoric acid oxygen ethyl propylene acid esters and methacrylate, 3-chloro-2-phosphoric acid oxygen propyl group acrylate and methacrylate or the like.

The example of cationic monomer comprises:

(ⅰ) by the deutero-monomer of acrylic or methacrylic acid, be commonly referred to as (first) acrylic acid hereinafter, and the quaternized epihalohydrin product that in alkyl, has the trialkylamine of 1-5 carbon atom, as (first) acrylic oxygen oxypropyl trimethyl ammonium chloride and (first) acrylic oxygen propyl group three second ammonium bromides;

(ⅱ) by the amine derivative of (first) acrylic acid or (first) acrylamide deutero-(first) acrylic acid amine derivative or (first) acrylamide with have C ₁～C ₄The dialkyl alkanolamine of alkyl, dimethyl amido ethyl (first) acrylate for example, diethyl amino ethyl group (first) acrylate, dimethylaminopropyl (first) acrylate, or dimethylaminopropyl (first) acrylamide;

(ⅲ) derivant of above-mentioned (ⅱ) set product, use acid by (1), example hydrochloric acid or lactic acid neutralization, (2) with halogenated alkyl as Methochloride, diethylaluminum monochloride, MB or ethyl iodide modification, (3) with a kind of halogenated fatty acid ester, as-monoxone ethyl ester or-modification of chloropropionic acid methyl ester, (4) with dialkylsulfates as dimethyl disulfide acid esters or the modification of diethyl sulfide acid esters.

In addition, the cation unsaturated monomer comprises the amine derivative of allyl compound, as chloride of diallyl dimethyl ammonium etc.

These cation unsaturated monomers can make its predecessor be modified as cation by its predecessor's mode polymerization by the polymerization of cation mode or they then, for example by quaternizing agent (as-ethyl chloroacetate, dimethyl sulfate or the like).

The example of ampholytic monomer, the derivant of bisexual ion purification that comprises the amine derivative of above mentioned (first) acrylic acid amine derivative or (first) acrylamide, for example, dimethyl aminoethyl (first) acrylate, dimethylaminopropyl (first) acrylamide is by halogenated soap, as-potassium chloroacetate ,-bromo-propionic acid sodium ,-chloroacetic amino methyl propylate ,-chloroacetic triethanolamine salt or the like; And the amine derivative of (first) acrylic acid or (first) acrylamide, use the propane sultone modification as mentioned above.

These ampholytic monomers, as above mentioned cationic monomer, can be by the polymerization of both sexes mode, perhaps, they can be converted into bisexual state then by its predecessor's mode polymerization.

Preferred ion monomer comprises acrylic acid, methacrylic acid, dimethyl amino ethyl methacrylate, quaternised dimethyl amino ethyl methacrylate, maleic acid, maleic anhydride half-ester, butenoic acid, itaconic acid, diallyl dimethyl ammonium chloride, polar vinyl heterocycle, as vinyl imidazole, vinylpyridine, styrene sulfonate, and composition thereof.Particularly preferred ion monomer comprises acrylic acid, dimethyl amino ethyl methacrylate, quaternised dimethyl amino ethyl methacrylate, the amine of listing above and acid salt with and composition thereof.

The polymer of the present invention 1%(weight of can having an appointment at least), ion monomer, preferably at least about 2%, preferred at least about 5%.

The resin of this paper also can contain the non-ionic monomer that comprises two kinds of high polar monomer and low polar monomers.

Ion exchange resin of the present invention generally contains have an appointment 1%-100% ion monomer and about 99% non-ionic monomer of 0%-, about 75% ion monomer of preferably about 2%-and about 98% non-ionic monomer of about 25%-, about 50% ion monomer of preferred about 5%-and about 95% non-ionic monomer of about 50%-.

The representative example of non-ionic monomer is C ₁-C ₂₄Alcohol, as methanol, ethanol, the 1-propanol, the 2-propanol, the 1-butanols, 2-methyl isophthalic acid-propanol, the 1-amylalcohol, the 2-amylalcohol, the 3-amylalcohol, 2-methyl-1-butene alcohol, 1-methyl isophthalic acid-butanols, 3-methyl isophthalic acid-butanols, 1-methyl-1-pentene alcohol, 2-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, the t-butanols, Hexalin, 2-ethyl-1-butanols, the 3-enanthol, benzylalcohol, sec-n-octyl alcohol, 6-methyl isophthalic acid-enanthol, 2-ethyl-1-hexanol, 3,-5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, the 1-dodecanol, the 1-hexadecanol, the acrylic or methacrylic acid esters of 1-octadecanol etc., have the preferably about 4-18 of its carbon atom average that has of alcohols of about 1-24 carbon atom, be more preferably about 4-12; Styrene; Chlorostyrene; Vinyl acetate such as vinylacetate; Vinyl chloride; Dichloroethylene; Acrylonitrile; α-Jia Jibenyixi; The t-butylstyrene; Butadiene; Cyclohexadiene; Ethylene; Propylene; Vinyltoluene; Alkoxyalkyl (first) acrylate is as methoxy ethyl (first) acrylate and butoxyethyl group (first) acrylate; And composition thereof.Other non-ionic monomer comprises for example allylic acrylate of the derivant of acrylate and methacrylate and methacrylate, the acrylate of cyclohexyl and methacrylate, and methacrylate, the acrylate of oil base and methacrylate, the acrylate of benzyl and methacrylate, tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate, glycol diacrylate and ethylene glycol bisthioglycolate (methacrylic acid) ester, 1,3-butanediol diacrylate and 1,3-butanediol two (methacrylic acid) ester N-[2-(2-methyl-4-oxopentyl), isobornyl methacrylate or the like.

Preferred non-ionic monomer comprise methacrylic acid just-butyl ester, methacrylic acid isobutyl, methacrylic acid 2-ethyl hexyl ester, methyl methacrylate, t-butylacrylic acid ester, t-butyl methyl acrylate and composition thereof.

The representative of polarity non-ionic monomer comprises acrylamide, N,N-DMAA, Methacrylamide, N-t-butyl acrylamide, methacrylonitrile, acrylamide, acrylate alcohol (C for example ₂-C ₈Acrylate alcohol, as hydroxyethyl acrylate, the acrylic acid hydroxypropyl ester); methacrylic acid hydroxyethyl ester, hydroxypropyl methacrylate, vinyl pyrrolidone, vinyl ethers; as ethylene methacrylic ether, acyl group lactone and vinylpyridine, allyl alcohol, vinyl alcohol and caprolactam.

The example of anion hair jelly resin is the copolymer of vinylacetate and butenoic acid, and the vinyl esters of the mono carboxylic acid of aliphatic series that the trimer of vinylacetate, butenoic acid and α-side chain are saturated is vinyl neodecanoic acid ester for example; With the copolymer of ethylene methacrylic ether and maleic anhydride (about 1: 1 of mol ratio), wherein this copolymer is with the radical of saturated aliphatic alcohol that contains 1-4 carbon atom, as ethanol or butanols 50% esterification; And acrylic copolymer and contain the trimer of acrylic or methacrylic acid as anionic group contains just like the copolymer part with methacrylic acid, butyl acrylate cores, methacrylic acid ethyl ester etc.Another example that can be applied to the acrylate copolymer of the present composition is the copolymer of tert-butyl group acrylamide, acrylic acid and acrylic acid ethyl ester.

The example that can be used for amphoteric resin of the present invention is the copolymer of octyl acrylamide/acrylate/metering system acid butyl amino-ethyl ester, described in United States Patent (USP) 4192861, as uncle's N-octyl acrylamide, methyl methacrylate, hydroxypropyl methacrylate, the polymer of acrylic acid and methacrylic acid tert-butyl group amino-ethyl ester, its molecular weight is suitable for the object of the invention.

The example of cation hair jelly resin is the acrylate monomer of amino-functional group, low alkylaminoalkyl as acrylic or methacrylic acid, as dimethylaminoethyl acrylate methyl base amino-ethyl ester, have compatible monomer such as N-vinyl pyrrolidone or alkyl methacrylate, as methyl methacrylate and methacrylic acid ethyl ester and alkyl acrylate, as the copolymer of methyl acrylate and butyl acrylate cores.The cationic polymer that contains the N-vinyl pyrrolidone is purchased by GAF Corp.

Also has other organic ion exchange resin, comprise carboxy methyl cellulose, the copolymer of PVA and butenoic acid, the copolymer of PVA and maleic anhydride, kayexalate, PVP/ methacrylic acid ethyl ester/methacrylic acid trimer, vinylacetate/butenoic acid/vinyl neodecanoate copolymer, octyl acrylamide/acrylate copolymer, the mono ethyl ester of poly-(ethylene methacrylic ether-maleic acid), and the copolymer of octyl acrylamide/acrylate/metering system acid butyl amino-ethyl ester.Also can use mixture of polymers.

Preferred ion exchange resin is the ionomer that contains silicone, the ionomer that contains silicone is described in, for example: EPO application 90307528.1(presses EPO application 0408311A2 on January 11st, 1991 and publishes, people such as Hayama) United States Patent (USP) 5061481(1991.10.29 announces people such as Suzuki), people such as United States Patent (USP) 5106609(Bolich, 1992.4.21 announce), people such as United States Patent (USP) 5100658(Bolich, 1992.3.31 announce), people such as United States Patent (USP) 5100657(Ansher-Jackson, 1992.3.31 announce), people such as United States Patent (USP) 5104646(Bolich, 1992.4.14 announce) United States Patent (USP) series No07/758319, (people such as Bolich, 1991.8.27 application) and people such as United States Patent (USP) series No.07/758320(Torgerson,, 1991.8.27 applies for), more than list in this paper all as a reference.

Preferably contain the silicone ionomer and contain an organic polymer main chain, vinyl backbone preferably, have a Tg or Tm, approximately more than-20 ℃, and will have weight average molecular weight at least about 500, be more preferably about 1000～about 100000, even preferably about again 2000～about 50000, most preferred about polysiloxane macromonomer of 5000～about 20000 connects skill to the main chain.Except above-mentioned graft copolymer, the polymer that contains silicone also comprises block copolymer, preferably contains up to about 50%(weight) one or more siloxane blocks and one or more non-silicone block (as acrylate or vinyl) of (being more preferably about 10%-about 40%).

Be used for this paper preferably contain the silicone ionomer be to make be mixed with final Haircare composition and when dry polymer be on good terms and be divided into discontinuous phase that contains the silicone part and the continuous phase that contains organic moiety.

The ionomer that contains silicone generally contains the above-mentioned monomer that contains the nonionic silicone with ion monomer, and also can contain the above-mentioned non-silicone non-ionic monomer that contains.The monomer that contains silicone also can be charged ionicly, and part or all of to the total charge density contribution of polymer.

The useful example that contains the silicone ionomer with and preparation method thereof be described in detail in United States Patent (USP) 4693935(Mazurek, 1987.9 months 15 announce) and the people .1988.3 month 1 announcement such as United States Patent (USP) 4728571(Clemens), these two pieces all to list in this paper for referencial use.

The silicone ionomer that contains of the present invention generally contains 0.01%～about 50% siliceous one monomers of having an appointment, and preferably about ion monomer of 0.5%～about 40% is more preferably about 2%～about 25%.

The monomer that contains silicone has following general formula;

X（Y）nSi（R）3-mZm

Wherein X be can with the vinyl of other monomer copolymerizable of polymer; Y is-the connection base of bivalence; R is-hydroxyl, low alkyl group be (as C ₁-C ₄), aryl, alkyl amino, alkaryl, hydrogen or alkoxyl; Z is that a monovalence siloxane polymerization that has at least about 500 number-average molecular weights partly and by above-mentioned organic polymer main chain hangs, and n is 0 or 1; And m is 1～3 integer.Certainly, Z does not react under polymerizing condition basically.The preferred weight average molecular weight of siliceous one monomers is at least about 1000, preferred about 1000～about 100000, be more preferably about 2000～about 50000, most preferred about 5000～about 20000, its preferred chemical formula is:

Wherein m be 1,2 or the preferred m=1 of 3(); P is 0 or 1; R is alkyl or hydrogen; Q is the integer of 2-6; X is

Wherein, R ²Be H or-the preferred R of COOH( ²Be hydrogen); R ³Be hydrogen, methyl or-CH ₂The preferred R of COOH( ³Be methyl); Z is

R ⁴, R ⁵, R ⁶Respectively be in alkyl, alkoxyl, alkyl amino, aryl, alkaryl, hydrogen or hydroxyl (preferred alkyl, be more preferably methyl); And r is at least about 5 integer, preferably about 10～about 1500, be more preferably about 70～about 700, most preferred is about 100～about 250.

The siliceous one monomers of the ionomer of this paper can be by the polymerization of siliceous one monomers form.Perhaps they can carry out polymerization with its predecessor who contains non-silicone, can add silicone then.For example, contain carboxylic acid ester monomer, acrylic acid for example can polymerization, reacts with the silicone compounds that contains that terminal epoxide group is arranged then.Generally, the result has above-mentioned chemical formula X(Y) nSi(R) in the polymer of the suitable structure of 3-mZm siliceous one monomers and attempt comprise at this paper.

Generally contain 0%～about 98%(preferably about 5%～about 98% in order to the silicone ionomer that preferably contains of the present invention, preferred about 50%～90%) non-ionic monomer, 1%～about 98%(preferably about 15%～about 80%) ion monomer, 0.1%～about the 50%(that has an appointment preferably about 0.5%～about 40%, most preferred about 2%～about 25%) monomer be the monomer that contains silicone.Contain the monomeric binding capacity of non-silicone preferably polymer about 50%～about 99%, preferred about 60%～about 99%, most preferred is about 75%～about 95%).

Being used for the example that contains the silicone ionomer of the present invention comprises following:

(ⅰ) acrylic acid/normal-butyl methacrylate/poly dimethyl silicone (PDMS) macromole-20000 molecular weight

(ⅱ) dimethylaminoethyl acrylate methyl base amino-ethyl ester/methacrylic acid isobutyl/methacrylic acid 2-ethyl hexyl ester/PDMS macromole-20000 molecular weight.

(ⅲ) t-butylacrylic acid ester/acrylic acid/PDMS macromole-10000 molecular weight.

(ⅳ) t-butylacrylic acid ester/acrylic acid/PDMS macromole-10000 molecular weight.

Known in the prior art, have the acid functionality, as the polymer of carboxylic group, usually so that the neutral form of small part is used the solubility with the promotion polymer.In addition, use neutral form to help Hairspray compositions with shampoo washing hair the time, to be easier in sending out, remove.In general, preferred about 10%～about 100%, preferred about 20%～about 90%, even most preferredly to neutralize for the acid monomer in about polymer of 40%～about 85%.

The alkali of any normally used organic or metal can be used for the neutralization of polymer.The special metal base of using in the present composition.Cation is that the hydroxide of alkali metal or alkaline-earth metal is the suitable nertralizer that is used for Hairspray compositions of the present invention.

The preferred nertralizer that is used for Hairspray compositions of the present invention is potassium hydroxide and sodium hydroxide.

The example that can be included in the suitable nertralizer of Hairspray compositions of the present invention comprises amine, amino alcohol particularly, as 2-amino-2-methyl-1, ammediol (AMPD), 2-amino-2-ethyl-1, ammediol (AEPD), 2-amino-2-methyl-1-propanol (AMP), 2-amino-1-butanols (AB), monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), monoisopropanolamine (MIPA), diisopropanolamine (DIPA) (DIPA), triisopropanolamine (TIPA) and dimethyl stearylamine (dimethyl stearamine(DMS), useful especially nertralizer is the mixture of amine and metal base.

Have alkaline degree of functionality, as amino group, polymer to small part with acid, neutral as hydrogen chloride is preferred.

In general, in this paper Hairspray compositions, anionic fluorinated surfactant is preferably being used in combination with cationic resin in a large number, and cation fluorine surfactant is not equally also with during resin anion (R.A.) is used in combination.

Liquid excipient

Hairspray compositions of the present invention also comprises a kind of liquid excipient.This can comprise and is usually used in the resin hair spray formulations those.The consumption of liquid excipient about 80%～about 99%, preferred about 85%～about 99% in Hairspray compositions.The consumption of preferred liquid excipient is about 90%～about 98% of a total composition.

The organic solvent that is applicable to the liquid excipient of this compositions is C ₁～C ₅Alkanol, carbitol, acetone and composition thereof.The preferred C that is used for the present composition ₁～C ₈Alkanol is C ₂～C ₄Monohydric alcohol, as ethanol, isopropyl alcohol and composition thereof.Water also is a kind of preferred solvent of liquid excipient that is used for Hairspray compositions of the present invention.

Preferably, the liquid excipient that is used for the present composition is to be selected from C ₁～C ₈Alkanol, water, carbitol, acetone and composition thereof.More preferably, the liquid excipient of the present composition is to be selected from water and C ₂～C ₄Monohydric alcohol such as ethanol and isopropyl alcohol and composition thereof.

In general, in liquid excipient, can not have water, or can liquid excipient all be water.Preferred liquid excipient is the mixture of a kind of water and organic solvent.

If make water and ORGANIC SOLVENT MIXTURES, water-ethanol or water-isopropyl alcohol-ethanol for example, the water content in the compositions are generally about 0.5%～about 99%, preferred about 5%～50% of total composition weight.In this mixture, the content of organic solvent is generally about 0.5%～about 99%, preferred about 50%～about 95% of total composition weight.

In general, advantage of the present invention is, owing to having used fluorine surfactant to improve sprayability in the present composition, having improved the sense of touch that spraying is implemented and improved under the hair fashioning situation of maintenance.

In the one side of invention, the resin of haircuting is extra high weight average molecular weight, and promptly its weight average molecular weight is higher than approximately 300000, particularly is higher than 500000.Have been found that, when these high molecular weight resins are used in combination with fluorine surfactant, can obtain surprising effective hair jelly performance, and fluorine surfactant in Hairspray compositions, provide resin is had can be effective especially aspect the characteristic of good atomization quality spraying, especially relate to and contain the macromolecular resin of haircuting of silicone, these resins preferably use the resin of the higher molecular weight that has been generally used for the usual resin of haircuting.This is very important, generally is difficult to prepare or has the product that can be applied through spraying of good atomization quality owing to this high molecular weight resin.

In another aspect of this invention, provide a kind of Hairspray compositions, it contains a kind of macromolecular ionic resin of haircuting of silicone, a kind of ionic fluorine surfactant and a kind of liquid excipient of containing.The weight average molecular weight that contains the macromolecular resin of haircuting of silicone can be any molecular weight of effectively haircuting that is suitable for providing, and in general, it is more generally at least about 70000, preferred at least about 100000 at least about 50000.Even under quite low molecular weight situation, the use fluorine surfactant can improve a sense of touch and not have infringement or infringement is arranged slightly sending out typing or sending out a maintenance performance.Moreover, at higher molecular weight, as be higher than 175000 especially about 200000 and the situation of Geng Gao under, can access and send out sense of touch and improve atomization quality sending out to keep improving under the performance.

In the present invention's preferred scheme in this respect, the weight average molecular weight of resin be about 70000～about 1000000, most preferred is about 70000～about 500000.

In general, the molecular weight upper limit of resin of the present invention only limits to that preparation suitable groups compound is had actual influence.It is about 10000000 that general molecular weight (average weight) will be not more than, and more generally is not more than approximately 3000000, preferably is not more than 1000000.

The present invention also has on the other hand, provides the hair jelly product that contains Hairspray compositions, and said composition contains the volatile organic solvent of reduced amounts, this organic solvent be used for packing into and the container of spray composite in.The volatile organic solvent Hairspray compositions of reduced amounts of the present invention contains the resin fluorine surfactant of haircuting, and the volatile organic solvent (not considering water for the object of the invention volatile organic solvent comprises volatile silicone liquid) that is not higher than 80%.The used volatile organic solvent of the present invention is meant the solvent with at least one carbon atom, and 20 ℃ of vapour pressures that have greater than 0.1mmHg.

In the volatile organic solvent hair jelly product of attenuating of the present invention, Hairspray compositions contains at least 10% water (weight).Also special consideration can contain at least about 11%, 12%, and 13%, 14%, 15% or the higher water yield.The volatile organic solvent compositions of the reduction amount of this paper can contain up to about 90%, and preferably up to about 70%, preferred height is about 60%, even is more preferably and is not more than about 50% the water yield; With about 10%～about 80%, preferred about 20%～about 80%, preferred about volatile organic solvent of 40%～about 80%.Considering also that compositions can be limited to contain is not more than about 75%, 65%, 55% or the volatile organic solvent of other amount.Compare with the Hairspray compositions that is purchased usually, if use fluorine surfactant, contain then very that the Hairspray compositions of high water content combines with volatile organic solvent, shockingly show the hair jelly performance of improvement, particularly send out a sense of touch improving under certain situation of haircuting.

Preferred reduction volatile organic solvent Hairspray compositions of the present invention contains 0.01%～about 2% the fluorine surfactant of having an appointment, it preferably is selected from cation fluorine surfactant, anionic fluorinated surfactant, both sexes fluorine surfactant, zwitterionic fluorine surfactant and composition thereof; About ionic resin of 0.1%～about 15% comprises having weight average molecular weight 300000 and 300000 above and be lower than 300000 below those, and comprises that those do not have silicone macromole part those, and particularly has partly those of silicone macromole; And liquid excipient, contain have an appointment 10%～about 45% water and about organic solvent of 55%～about 80%, preferably be selected from ethanol, isopropyl alcohol and its mixture.

The consumption of fluorine surfactant, in general, as mentioned above.But can think, the fluorine surfactant that must use particular amount is to reach the performance of improving hair jelly, or reach optimum performance, to specific Hairspray compositions can be different, this is decided by various factors, comprises the particular type and the molecular weight thereof of selected resin, and the content in compositions, specific fluorine surfactant, the type of water content and volatile organic solvent and content and existing optional components in system.In general, need the fluorine surfactant of higher amount to reach the benefit of performance, as reducing molecular resin amount and/or water content.Generally, the compositions of the present invention fluorine surfactant that will contain effective dose at least with improve to desired level decide outbreak with or improve the sense of touch of sending out of atomization quality

The surfactant of nonfluorinated

Randomly, Hairspray compositions can contain the surfactant of one or more nonfluorinateds.Usually, if used this non-fluorinated surfactants the total amount used can be composition total weight about 0.01%～about 2%, preferred about 0.01%～about 1.5% and be more preferably about 0.01%～about 1%.

Can use various non-fluorinated surfactants, comprise anionic, cationic, amphoteric and zwitterionic surfactant.

Anion surfactant comprises, for example, and alkyl and alkenyl sulfate; The sulfate of alkyl and alkenyl ethoxylation (preferably having 1～10 average degree of ethoxylation) succinamic acid ester surfactant is as the dialkyl of alkyl sulphosuccinamate and 2-Sulfosuccinic acid; The fatty acid ester of neutral isethionic acid and alkyl and olefin sulfonate comprise as alkene sulfonate and β-oxyalkyl chain alkyl sulfonate.The preferably sulfate such as the C of alkyl and alkenyl sulfate and alkyl and alkenyl ethoxyquin ₁₂～C ₁₈Sulfate and have 1～about 6 sulfate of the ethoxyquin of the ethoxyquin degree of 1-about 4 preferably.As lauryl sulfate and laureth(30) sodium salt and the ammonium salt of sulfate.

Amphoteric surfactant comprise can be broadly described the derivant and so on of the secondary and tertiary amine of aliphatic series, wherein aliphatic group can be a straight or branched, one of them aliphatic substituent group contains 8～about 18 carbon atoms of having an appointment, and one contain the water-soluble group of an anion, as carboxyl, sulfonic group, sulfate, phosphate or phosphonate group.Examples of compounds in this definition is a 3-dodecane alanine sodium; the N-alkyl taurine; report according to United States Patent (USP) 2658072; with the reaction of dodecyl amine and hydroxyethyl sulfonate and preparation; N-senior alkyl aspartic acid; as producing those according to the report of United States Patent (USP) 2438091, and sell and be described in product in the United States Patent (USP) 2528378 with trade name " Miranol ".Other comprises alkyl (C preferably ₆～C ₂₂, most preferred is C ₈～C ₁₂) the both sexes glycinate, alkyl (C preferably ₆～C ₂₂Most preferred is C ₈～C ₁₂), the both sexes propionate, and composition thereof.

The example that is used for the suitable zwitterionic surfactant of this compositions can be the derivant that extensively is described as aliphatic quaternary ammonium, phosphorus and sulfonium compound, wherein aliphatic group can be a straight or branched, and one of them aliphatic substituent group contain have an appointment 8～18 carbon atoms another contain an anionic water-soluble group as, carboxyl, sulfonic group, sulfate, phosphate or phosphonate group.The general formula of these chemical compounds is:

R wherein ₂The alkyl that contains about 8～about 18 carbon atoms, alkenyl or hydroxyalkyl group, 0～about 10 ethylene oxide moieties and 0～1 glyceryl part; Y is selected from nitrogen, p and s atom; R ³Be alkyl or the monohydroxy alkyl that contains 1～about 3 carbon atoms; X is 1 when Y is sulfur or phosphorus, and x is 1 or 2 when Y is nitrogen, R ⁴Be the alkenyl of 1～about 4 carbon atoms or hydroxyl alkenyl and Z is selected from carboxylate, sulfonate, sulfate, phosphonate and phosphatic group.Zwitterionic kind comprises alkyl amino sulfonate, alkyl betaine and alkyl amido betanin.

The cationic surfactant that is used for the present composition contains amino or quaternary ammonium hydrophilic segment usually, and in the time of in being dissolved in aqueous phase composition of the present invention, they are positive charges.The cationic surfactant that is used for herein is disclosed in following document, and these documents are all listed in for referencial use: M.C.Pullishing Co.McCutcheon ' s Detergents ﹠amp; Emulsifiers(North American edition 1979); People such as Schwartz, Surface Active Agents, Their Chemistry and Technology, New York; Interscience Publishers, 1949; The United States Patent (USP) 3155591 of the Hilfer that on November 3rd, 1964 announced; The people's such as Laughlin of December in 1975 announcement on the 30th United States Patent (USP) 3929678; The people's such as Bailey that on May 25th, 1976 announced United States Patent (USP) 3959461; The Bolich that announce June 7 nineteen eighty-three, the United States Patent (USP) 4387090 of Jr.

Be to have those of following general formula used herein containing in the quaternary ammonium cation surfactant:

R wherein ₁Be the aliphatic group of 1～22 carbon atom, or the aromatic group of 12～22 carbon atoms, aryl or alkylaryl group; R ₂It is the aliphatic group of 1～22 carbon atom; R ₃And R ₄Respectively be the alkyl group of 1～3 carbon atom, X is the anion that is selected from halogen, acetate, phosphate, nitrato and alkyl sulfide acidic group group.Aliphatic group de-carbon and hydrogen atom are outer can to contain ehter bond and other group such as acylamino-.The quaternary ammonium salt of useful herein other is a bi-quaternary ammonium salt.

Preferred quaternary ammonium salt comprises the dialkyl dimethyl ammonium chloride, 12～22 carbon atoms are wherein arranged in alkyl group and is by long-chain fatty acid, as obtaining in the hydrogenant tallow fatty acid.(in the quaternary ammonium compound that tallow fatty acid produces, R ₁And R ₂Mainly be 16～18 carbon atoms).

The primary, the salt of the second month in a season, uncle's fatty amine also is to be used for suitable cationic surfactants of the present invention.The alkyl group of these amine preferably has 12～22 carbon atoms, and can be that replace or unsubstituted.Secondary and tertiary amine is preferred, and tertiary amine is preferred especially.The useful this amine of the present invention comprises, stearamidopropyldime.hylamine, diethylamino ethyl stearmide, dimethyl stearylamine, dimethyl bean amine (soyamine), bean amine, (5 moles of E.O) stearylamine of tetradecylamine, tridecyl amine, ethyl stearic amine, N-tallow propane diamidogen ethoxyquin, dihydroxy ethyl stearic amine and larane base mountain Yu base amine.The United States Patent (USP) 4275055(that useful in the present invention cationic amine surfactant is disclosed in the Nachtigal that announced on June 23rd, 1981 lists in as a reference at this.

The salt of suitable cationic surfactants comprises halogen, acetate, phosphate, nitrate, citrate, lactate and alkyl sulfate.

Non-ionic surface active agent also can include in this compositions.Preferably, non-ionic surface active agent has the average HLB(hydrophil lipophil balance value that is less than or equals about 7).

Measure the method for HLB and know in the prior art, any this method may be used to the mensuration of HLB.The description of HLB system and HLB assay method are described in " The HLB System:a time Saving guide to emulsifier selection " ICI Americas Inc; Wilmington, Delaware; 1976.

Ionic surfactant pack is drawn together the condensation substance (C preferably of the polyethylene oxygen of alkylphenol ₆～C ₁₂Alkyl, about ethoxyquin degree of 1～about 6) condensed products of oxirane and expoxy propane and reacting ethylenediamine product, the condensed products of aliphatic alcohol and oxirane, long-chain (is general C ₁₂～C ₂₂) tertiary amino oxides, the long chain tertiary phosphine oxide contains an a chain alkyl or hydroxyalkyl group and a short chain (preferred C ₁-C ₃) dialkyl sulphoxide of group, silicone copolyol and have C ₈-C ₂₂The C of acyl moiety acid ₁-C ₄Alkanolamide.

The ionic strength modifier system

Randomly, Hairspray compositions of the present invention can contain a kind of on-surface-active ionic strength modifier system of effective dose to reduce the viscosity of Hairspray compositions.If use, then the content of ionic strength modifier in this compositions is at least about 0.01% of composition weight.Its upper limit is decided by the maximum of ionic strength modifier, and this amount can exist in the specific compositions of this paper and make the resin of haircuting still keep dissolving or dispersion.The ionic strength increase that one skilled in the art will understand that compositions then resin or no longer keeps dissolving or disperses the most at last by separating out in the solution in liquid-carrier.The upper limit of ionic strength modifier system is along with existing specific ion intensity modifier in compositions, liquid excipient, resin, and other composition and difference.Therefore, for example for the compositions of the compositions that the liquid excipient that contains low amounts of water the is arranged excipient more more than water content, the maximum of the ionic strength modifier that it is used just can be hanged down.In general, compositions will contain the 4%(weight of having an appointment), or ionic strength modifier still less, more generally about 2% or still less and usually about 1% or still less.Preferentially, this paper compositions will contain has an appointment 0.01%～0.5%, more preferably about ionic strength modifier system of 0.01%～about 1%.

The ionic strength modifier system comprises monomeric cation and anionic mixture.The ion of the ionic strength modifier system of this paper is non-surface active, and promptly they reduce surface tension not obviously.Be purpose of the present invention, on-surface-active is meant those at 0.5% concentration of aqueous solution, and capillary reduction is not more than 5.0 dyne/cm ²Ion.Usually, the ion characteristic of the ionic strength modifier system of this paper is in organic heterochain of any fat chain or straight or branched, and every electric charge is the highest to have 4 or a carbon atom still less, preferably 2 or carbon atom still less.

The ionic strength modifier system comprises the monomer ion of acid-base reaction product types.Therefore, the ion OH of alkali and acid ^-And H ⁺They do not constitute the part of this paper ionic strength modifier, though can exist in compositions.The ion of this paper is to exist with dissociated ion in compositions by them, i.e. the form that exists with decomposed form and mix compositions.The ion that there is no need all to add all exists with dissociated ion in compositions, is dissolved or decomposition in compositions but must have part at least.Ionic strength modifier can mix to be sent out in the Hairstyling composition, for example adds soluble salt, or adds mixture or its conjugate of bronsted lowry acids and bases bronsted lowry.All listing the anion of ionic strength modifier system and cation in this compositions is necessary aspect of the present invention.

The suitable cation that uses comprises for example alkali metal, as lithium, sodium and potassium; And alkaline-earth metal such as magnesium, calcium and strontium.Preferred bivalent cation is a magnesium.Preferred monovalent metallic ion is lithium, sodium and potassium, particularly sodium and potassium.The appropriate method that the present invention joins in the compositions comprises, for example, presses alkali and adds, and as hydroxide, sodium hydroxide and potassium hydroxide, and by the salt adding that is dissolved in liquid-carrier, the anionic salt of monomer as described below.

Other suitable cation comprises organic ion, as quaternary ammonium ion and cationic amine, as ammonium, single, two one and three monoethanolamines, triethylamine, morpholine, aminomethyl propanol (AMP), aminoethyl propylene glycol etc.Preferred ammonium and amine are that form such as the hydrogen chloride salt by salt provides.

Operable monomer anion comprise halide ion as, chloride, fluoride, bromide and iodide, particularly chloride, sulfate, sulfovinate, Methylsulfate, cyclohexyl-n-sulfonate, thiosulfate, toluene fulfonate, xylenesulfonate, citrate, nitrate, bicarbonate, adipate, succinate, glucide hydrochlorate, benzoate, lactate, borate, isethionate, tartrate and other can be the monomer anion of decomposed form in sending out Hairstyling composition.Anion for example with the form of acid or salt, can add in this paper compositions, and these acid or salt are to be partly dissolved in the liquid excipient at least, as the sodium or the potassium salt of acetate, citrate, nitrate, chloride, sulfate etc.Preferably, these salt are to be dissolved in excipient fully.

Use ionic strength modifier particularly useful in reducing the volatile organic solvent compositions, those uses most particularly contain the macromolecular polymer of silicone.

Hairspray compositions

Hairspray compositions of the present invention can be disperseed by container, and this container is aerosol dispersion device or pump spraying disperser.This disperser is a container, to those skilled in the art be know and also can be commercial by each manufacturer, comprise American National Can Corp. and Continental Can Corp.

When Hairspray compositions is disperseed by the pressure aerosol container, comprise that a kind of propellant of one or more common known aerosol propellants can be used for advancing compositions.The suitable propellant that uses can be to be generally used for aerocolloidal any liquid gas.

The suitable propellant that uses is the volatile hydrocarbon propellant, and it can comprise the liquefaction lower hydrocarbon of 3～4 carbon atoms, as propane, butane, iso-butane.Other suitable propellant be hydrogen fluorine carbon thing as 1,2-Difluoroethane (Hydrofluorocarbon 152A) is supplied with Dymel 152A by Dupont.Other example of propellant is a dimethyl ether, nitrogen, carbon dioxide, nitrous oxide and atmosphere.

Preferably hydrocarbon, particularly iso-butane can use separately or mix with other hydrocarbon phase and use.

Aerosol propellants can mix with this compositions, and wants blended propelling dosage to be controlled by the regular element that the aerosol prior art is known.Generally, to liquable propellant, the consumption of propellant be total composition weight about 10%～about 60%, preferably about 15%～about 50% of total composition weight.

Perhaps, can use the pressurized aerosol disperser at this moment propellant be to separate with contacting of Hairspray compositions, as two types, sell by trade name SEPRO by Americal National Can Corp every jar.

Other suitable aerosol dispersion device is to be that compressed air is those of feature with the propellant, compressed air can be charged into disperser before use by pump or suitable device.This disperser is described in United States Patent (USP) 4077441(1978 March 7, Olofsson) and 4850577(1989 July 25, TerStege), all list in this for two pieces, with for referencial use, and in people such as U.S. series application No07/839648(Gosselin, application on February 21st, 1992) also list in this as a reference.The compressed air aerosol container also is suitable at present commercially available, by Procter ﹠amp; Gamble Conpany is by its trade name VIDAL SASSOON AIRSPRY ^RThe hair jelly supply.

Common non-aerosol pump spraying disperser as aerosol apparatus, also can use.

Hair spray formulations of the present invention can randomly contain hair jelly auxiliary agent commonly used.Generally, all auxiliary agent can contain the 0.05%～about 5%(weight of having an appointment), preferably about 0.1%～about 3%(weight).This optional adjuvants commonly used is known this area professional, comprises for example various lanoline chemical compounds of plasticizer, silicone, softening agent, lubricant and penetrating agent, protein hydrolysate and other protein derivatives; Ethylene adduct and polyoxyethylene cholesterol; Pigment, hair dye and other coloring agent; Sunscreen; And spice.

Preparation method

Hairspray compositions of the present invention can use common preparation and hybrid technology.Preferably before adding, fluorine surfactant given with water and mixing.If water not in compositions then preferably gives fluorine surfactant and mixing with organic solvent such as ethanol.The preparation of compositions method of hair jelly of the present invention is described in following examples in more detail.

Using method

Hairspray compositions of the present invention uses in due form to provide the present invention to send out the advantage of typing/maintenance.This method generally comprises the product of using effective dose before hair fixing and/or later on dry and/or moistening hair slightly." effective dose " is meant the length of considering hair and characteristic, keeps and the amount of the effect of typing enough to provide desired.Use the present composition in such a way, can keep hair style best when showing good spraying ability.

Following examples further specify preferred version within the scope of the present invention.Routine embodiment only be used for illustrative purposes, rather than the restriction the present invention, can do a lot of improvement to the present invention without departing from the spirit and scope of the present invention.

Embodiment 1

The Hairspray compositions of the present invention that is suitable for pump spraying disperser prepares by following method:

Form weight %

Ethanol, 200 proof-spirit degree 78.92%

Isopropyl alcohol 10.00%

Resin ¹3.00%

KOH（45%） ²0.88%

DRO water ³7.00%

Fluorad FC-109（25%） ⁴0.20%

1 60% acrylic acid tertiary butyl ester/20% acrylic acid/20% silicone macromole (weight average molecular weight=10000) has about 690000 weight average molecular weight,

2 potassium hydroxide solutions, the water and the less important composition (minors) that contain 45% potassium hydroxide and 55% are provided by Fisher Scientific.

3 pairs of anti-phase infiltration waters

4 Fluorad FC-109

Provide by 3M, contain 25% fluoroalkyl carboxylic acid potassium (a kind of anionic fluorinated surfactant), 12% propanol, 2% ethanol and 61% water and less important composition.

The hair spray formulations of embodiment 1 gives mixture and prepares by resin is made in isopropyl alcohol.Isopropyl alcohol is given mixture be added in the ethanol, neutralize with potassium hydroxide solution then.Prepare the mixture that gives of fluorine surfactant and water then, and join neutral giving in the mixture.Can add other auxiliary agent then, as spice.Use a kind of magnetic or air agitator mixing composition, up to resin dissolves, general about 1～2 hour.

The embodiment II

Be applicable to the Hairspray compositions of the present invention of pump spraying disperser, press following preparation:

Form weight %

Ethanol, 200 proof-spirit degree 89.45%

Resin ¹3.00%

KOH（45%） 0.88%

DRO water 7.00%

Zonyl FSK （47%） ²0.11%

The silicone macromole of 1 60% acrylic acid tertiary butyl ester/20% acrylic acid/20% weight average mw=10000 has about 690000 weight average molecular weight.

2 ZonYl FSK

Contain 47% according to chemical formula R _fCH ₂CH(OCOCH ₃) CH ₂N ⁺(CH ₃) ₂CH ₂CO - ₂, R wherein _f=F(CF ₂CF ₂) _3-8Fluorine surfactant and 53% acetic acid and submember, have amphion character, supply by Dupont.

Compositions is pressed embodiment 1 preparation.

The embodiment III

A kind of Hairspray compositions of the present invention that is applicable to pump spraying disperser is by following preparation.

Form weight %

Ethanol, 200 proof-spirit degree 79.05%

Resin ¹2.60%

KOH（45%） 0.75%

DRO water 7.00%

Fluorad FC-120

（25%） ²0.20%

The silicone macromole of 1 60% tert-butyl acrylate/20% acrylic acid/20% weight average mw=10000 has weight average molecular weight about 800000.

2 Fluorad FC-120 By the 3M supply, have anionic nature and contain 25% blended perfluoroalkyl ichthyodin, 37.5% ethanol and 37.5% water and less important composition.

The hair spray formulations of embodiment III prepares in the alcoholic acid mixture that gives by preparing a kind of resin.Then with giving mixture with ethanol in the potassium hydroxide solution.Prepare giving mixture and being added to neutral giving in the mixture of fluorine surfactant and water then.Can add other auxiliary agent then, as spice.Use magnetic or air agitator mix and form, up to resin dissolves, general about 1～2 hour.

The embodiment IV

A kind of Hairspray compositions of the present invention that is applicable to pump spraying disperser, by being prepared as follows:

Form weight %

Ethanol, 200 proof-spirit degree 79.10%

Isopropyl alcohol 10.40%

Resin ¹2.60%

KOH（45%） 0.75%

DRO water 7.00%

Fluorad FC-120

（25%） 0.10%

Zonyl FSK（47%） 0.05%

The silicone macromole of 1 60% tert-butyl acrylate/20% acrylic acid/20% weight average mw=10000 has about 800000 weight average molecular weight.

Compositions is pressed the preparation of embodiment I.

The embodiment V

Form weight %

Ethanol, 200 proof-spirit degree 78.86%

Isopropyl alcohol 10.40%

Resin ¹2.60%

KOH（45%） 0.69%

DRO water 7.00%

Fluorad FC-120 （25%） 0.40%

Zonyl FSK

（47%） 0.05%

The silicone macromole of 1 60% tert-butyl acrylate/20% acrylic acid/20% weight average: mw=10000 has about 1700000 weight average molecular weight.

Compositions is pressed the preparation of embodiment I.

The embodiment VI

Form weight %

Ethanol, 200 proof-spirit degree 89.55%

Resin ¹2.60%

KOH（45%） 0.75%

DRO water 7.00%

Fluorad FC-135

（50%） ²0.10%

The silicone macromole of 1 60% tert-butyl acrylate/20% acrylic acid/20% weight average mw=20000 has about 800000 weight average molecular weight.

2 Fluorad FC-135

By the 3M supply, have anionic nature, contain 20% blended perfluoroalkyl ichthyodin, 37.5% ethanol and 37.5% water and less important composition.

Said composition is pressed the preparation of embodiment II.

The embodiment VII

Form weight %

Ethanol, 200 proof-spirit degree 90.20%

Resin ¹2.00%

KOH（45%） 0.60%

DRO water 7.00%

Fluorad FC-100

（25%） ²0.20%

2 Fluorad FC-100

By the 3M supply, have amphotericity, and contain 25% blended perfluoroalkyl ichthyodin, 37.5% ethanol and 37.5% water and less important composition.

Said composition is pressed the preparation of embodiment II.

The embodiment VIII

Form weight %

Ethanol, 200 proof-spirit degree 71.18%

Isopropyl alcohol 9.52%

Resin ¹2.38%

KOH（45%） 0.59%

DRO water 16.19%

Zonyl TBS

（35%） ²0.14%

2 Zonyl TBS

By the Dupont supply, have anionic nature, and contain 30～35% perfluoroalkyl sulfonic acid, ammonium salt, 2.4% acetic acid and 65%～70% water and less important composition.

Said composition is pressed the preparation of embodiment I.

The embodiment IX

Form weight %

Ethanol, 200 proof-spirit degree 80.00%

Resin ¹2.38%

KOH（45%） 0.59%

DRO water 16.94%

Zonyl FSK

（47%） 0.10%

Said composition is pressed the preparation of embodiment II.

The embodiment X

A kind of Hairspray compositions of the present invention that is applicable to pump spraying disperser, press following preparation:

Form weight %

Ethanol, 200 proof-spirit degree 71.20%

Isopropyl alcohol 9.52%

Resin ¹2.38%

KOH（45%） 0.59%

DRO water 16.19%

Zonyl FSK

（47%） 0.05%

Zonyl TBS

（35%） 0.07%

The silicone macromole of 1 75% ethyl methacrylate/20% acrylic acid/20% acrylic acid/5% weight average mw=10000 has about 1000000 weight average molecular weight.

Said composition is pressed the preparation of embodiment I.

The embodiment XI

Form weight %

Ethanol, 200 proof-spirit degree 78.99%

Isopropyl alcohol 10.40%

Resin ¹2.60%

AMP ²0.16%

KOH（45%） 0.63%

DRO water 7.00%

Fluorad FC-120

（25%） 0.10%

Zonyl FSK （47%） 0.05%

Zonyl TBS

（35%） 0.07%

The silicone macromole of 1 60% tert-butyl acrylate/20% acrylic acid/20% weight average mw=10000 has about 860000 weight average molecular weight.

2 amino methyl propanol

Said composition is pressed the preparation of embodiment I.

The embodiment XII

Form weight %

Ethanol, 200 proof-spirit degree 96.06%

Resin ¹3.33%

AMP 0.41%

Fluorad FC-120 ^R（25%） 0.20%

The silicone macromole of 1 60% tert-butyl acrylate/20% acrylic acid/20% weight average mw=10000 has about 624000 weight average molecular weight.

Said composition is pressed the preparation of embodiment I.

Embodiment X III

Form weight %

Ethanol, 200 proof-spirit degree 80.00%

Resin ¹2.60%

KOH（45%） 0.44%

DRO water 16.00%

Fluorad FC-120 （25%） 0.76%

Spice 0.20%

The silicone macromole of 1 60% tert-butyl acrylate/20% acrylic acid/20% weight average mw=10000 has about 2000000 weight average molecular weight.

Said composition is pressed the preparation of embodiment I, except fluorine surfactant is to give mixed rather than the isopropyl alcohol with ethanol.

Embodiment X IV

Form weight %

Ethanol, 200 proof-spirit degree 70.73%

Isopropyl alcohol 8.80%

Resin ¹2.20%

KOH（45%） 0.37%

DRO water 17.00%

AE ₃S（28%） ²0.30%

Fluorad FC-100

（25%） 0.40%

Spice 0.20%

2 Ammonium Laureth Sulfate solution contain 28%laureth ammonium sulfate, and 3 moles of ethoxy molecules and 72% water and submember are supplied by Stepan.

Said composition is pressed the preparation of embodiment I.

Embodiment X V

Form weight %

Ethanol, 200 proof-spirit degree 79.00%

Resin ¹4.00%

KOH（45%） 0.84%

DRO water 15.86%

Dioctylis sulfosuccinas natricus

²0.25%

Fluorad FC-120 0.20%

The silicone macromole of 1 60% tert-butyl acrylate/20% acrylic acid/20% weight average mw=10000 has about 500000 weight average molecular weight.

2 dioctylis sulfosuccinas natricuses

, a kind of diisooctyl (diioctyl) sulphur sodium succinate surfactant is buied by 75% living solution in water and ethanol by American Cyanamid.

Said composition is pressed the preparation of embodiment II.

Embodiment X VI

A kind of Hairspray compositions of the present invention that is applicable to the aerosol dispersion device, press following preparation:

Form weight %

Ethanol, 200 proof-spirit degree 96.38%

Resin ¹3.00%

AMP ²0.37%

Zonyl FSJ （40%） ³0.25%

The silicone macromole of 1 60% tert-butyl acrylate/20% acrylic acid/20% weight average mw=10000 has about 690000 weight average molecular weight.

2 aminomethyl propanols

3 Zonyl FSJ

By the Dupont supply, have anionic nature, and contain 40% blended single and two fluoroalkyl phosphates, ammonium salt, coordination is bonded mutually with the aliphatic quaternary ammonium metilsulfate, 15% isopropyl alcohol and 40～45% water.

Said composition is pressed the preparation of embodiment I, except fluorine surfactant is to give with ethanol mixing rather than mixing with isopropyl alcohol.

Embodiment X VII-XX

Prepared following Hairspray compositions, can be scattered in the non-aerosol, the pump automiser spray is with compressed air, pump automiser spray or combine with chemical propellant at common aerosol container:

Form embodiment ^#(weight %)

XVII XVIII XIX XX

Ethanol, 200 proof-spirits 78.76 78.00 78.00 78.76

Water 15.55 14.15 14.62 16.14

Fluorad FC-120 (25% activity) 0.14 0.14 0.14 0.14

Amphomer ¹4.00 5.20 4.50 3.5

Aminomethyl propanol (AMP) 0.66 0.86 0.74 0.58

The diformazan silicone copolyol

(Dimethicone?Copolyol) 0.50 0.10 0.25 0.24

Ring first silicone (Cyclomethicone) 0.24 1.00 1.00 0.44

Spice and other minor consistuent 0.16 0.56 0.75 0.15

1 Amphomer

The copolymer of octyl acrylamide (octoylacrylamide)/acrylate/methacrylic acid fourth amino ethyl ester is by National Starch and Chemical Co(Bridgewater NJ.USA) buy heavily even mw about 70000.

All above-mentioned composition has good pulverability when being sprayed to send out when going up, and sends out sense of touch and can keep hair style.

In the foregoing description and the present composition, use the grafted molding resin of silicone macromole, can require the purification molding resin by removing nonreactive siliceous one monomers, and silicone macromole-graft polymers has the viscosity of about 10000000 centistokes and littler viscosity at 25 ℃.For example this can be undertaken by hexane extraction.After by its reaction dissolvent dry resin, the hexane extraction of product can be carried out in product by adding excessive hexane, and is heated to the Tg near the non-silicone part of polymer.Under this temperature, keep this mixture and stir about 30 minutes cool to room temperature then.By vacuum draw to remove hexane.Preferably carry out the circulation of secondary hexane extraction again with quadrat method by above-mentioned.After circulation for the third time, remove by distillation and vacuum drying with the residual hexane that product stays.

Claims

1, a kind of Hairspray compositions is characterized in that comprising:

A) the ionic fluorine surfactant of about 0.01%～about 2% (weight);

B) about 0.1%～about 15% have weight average molecular weight at least about 300000 ionic resin;

C) a kind of liquid excipient.

2, a kind of Hairspray compositions according to claim 1, wherein ionic fluorine surfactant be selected from following:

ⅰ) cation fluorine surfactant;

ⅱ) anionic fluorinated surfactant;

ⅲ) both sexes fluorine surfactant;

ⅳ) zwitterionic fluorine surfactant; With

V) its mixture.

3, a kind of Hairspray compositions according to claim 1, wherein said ion fluorine surfactant comprise a kind of anionic fluorinated surfactant and a kind of both sexes or zwitterionic fluorine surfactant or both mixture.

4, a kind of Hairspray compositions according to claim 1, wherein said ion exchange resin comprise about 2%～about 75% ion monomer and about 25%～98% non-ionic monomer.

5, a kind of Hairspray compositions according to claim 4, wherein said ionic monomer is an acrylic acid, methacrylic acid, dimethylaminoethyl acrylate methyl base amino-ethyl ester, quaternary ammoniated dimethylaminoethyl acrylate methyl base amino-ethyl ester, maleic acid, the half ester of maleic anhydride, butenoic acid, the itaconic acid, diallyl dimethyl ammonium chloride, vinylpyridine, vinyl imidazole, styrene sulfonate and composition thereof.

6, a kind of liquid Hairspray compositions according to claim 5, wherein said non-ionic monomer is to be selected from C ₁～C ₂₄The acrylate of alcohol, C ₁～C ₂₄The methacrylate of alcohol, styrene, polystyrene macromolecular, vinylacetate, vinyl chloride, the vinyl propionic ester, vinylidene chloride, α-Jia Jibenyixi, t-butylstyrene, butadiene, cyclohexadiene, ethylene, propylene, vinyltoluene and composition thereof.

7, a kind of Hairspray compositions is characterized in that comprising:

A) ion fluorine surfactant about 0.01～about 2%(weight);

B) about 0.1%～about 15% have a ion exchange resin at least about 300000 weight average molecular weight, described ion exchange resin contains the monomer of silicone, wherein when composition dries, send out the continuous phase that molding resin is separated into the discontinuous phase of the silicone part that comprises described resin and comprises non-silicone part; And

C) liquid excipient.

8, a kind of a kind of liquid according to claim 7 is sent out Hairstyling composition, and wherein said polymer comprises the siliceous one monomers at least about 0.5%.

9, a kind of liquid according to claim 8 is sent out Hairstyling composition, contains have an appointment 5%～about 95% ion monomer and about 5%～95% non-ionic monomer.

10, a kind of liquid according to claim 9 is sent out Hairstyling composition, and wherein said compositions contains 2%～25% the siliceous one monomers of having an appointment.

11, a kind of Hairspray compositions is characterized in that comprising:

A) ion fluorine surfactant about 0.01～about 2%(weight);

B) about 0.1%～about 15% have a ion exchange resin at least about 300000 weight average molecular weight, the described chemical formula that contains the silicone macromonomer is:

X（Y）nSi（R）3-mZm

Wherein X is-vinyl group; Y is a bivalence linking base group; R is a hydrogen, hydroxyl, low alkyl group, aryl, alkaryl, alkyl amino or alkoxyl; Z has the monovalence siloxane polymerization part of having divided amount at least about 500 number averages; N is 0 or 1; M is 1～3 integer; And

C) liquid excipient.

12, a kind of liquid Hairspray compositions according to claim 11 wherein saidly contains the silicone macromonomer and is:

Wherein m is 1,2 or 3, and p is 0 or 1, and q is 2～6 integer, and X is

R ¹Be-H or-COOH, R ²Be-H-CH ₃, or CH ₂COOH, R ⁴Be alkyl, alkoxyl, alkyl amino, aryl, alkylaryl, hydrogen or hydroxyl, and Z is

Wherein r is the integer at least about 5,

13, a kind of liquid Hairspray compositions according to claim 7, wherein said ion monomer is an acrylic acid, methacrylic acid, dimethylaminoethyl acrylate methyl base amino-ethyl ester, quaternised dimethylaminoethyl acrylate methyl base amino-ethyl ester, maleic acid, the half ester of maleic anhydride, butenoic acid, the itaconic acid, diallyl dimethyl ammonium chloride, vinylpyridine, vinyl imidazole, styrene sulfonate and composition thereof.

14, a kind of liquid Hairspray compositions according to claim 13, wherein said polymer contain 15%～about 80% the described ion monomer of having an appointment, about non-ionic monomer of 50%～about 90%, and this monomer is selected from C ₁～C ₂₄The acrylate of alcohol, C ₁～C ₂₄The methacrylate of alcohol, styrene, polystyrene macromolecular, vinylacetate, vinyl chloride, vinyl propionic ester, vinylidene chloride, α-Jia Jibenyixi, t-butylstyrene, butadiene, cyclohexadiene, ethylene, propylene, vinyltoluene and composition thereof and about described siliceous one monomers of 2%～about 25%.

15, a kind of liquid Hairspray compositions according to claim 12, wherein said ion monomer is an acrylic acid, methacrylic acid, dimethylaminoethyl acrylate methyl base amino-ethyl ester, quaternised dimethylaminoethyl acrylate methyl base aminoethyl ester, maleic acid, the half ester of maleic anhydride, butenoic acid, the itaconic acid, diallyl dimethyl ammonium chloride, vinylpyridine, vinyl imidazole, styrene sulfonate or its mixture.

16, a kind of liquid Hairspray compositions according to claim 15, wherein said polymer comprises 15%～80% described ion monomer, about non-ionic monomer of 50%～about 90%, it is selected from C ₁～C ₂₄The acrylate of alcohol, C ₁～C ₂₄The methacrylate of alcohol, styrene, polystyrene macromolecular, vinylacetate, vinyl chloride, vinyl propionic ester, vinylidene chloride, α-Jia Jibenyixi, t-butylstyrene, butadiene, cyclohexadiene, ethylene, propylene, vinyltoluene and its mixture, and about 20%～about 25% described siliceous one monomers.

17, a kind of Hairspray compositions according to claim 1, its intermediate ion fluorine surfactant is to be selected from:

1) fluorinated alkyl quaternary ammonium iodide;

2) single and two perfluoroalkyl phosphate, single or two fluoroalkyl phosphates, coordination is bonded mutually with the aliphatic quaternary ammonium metilsulfate; Perfluoroalkyl sulfonate; Telomer phosphate diethanolamine salt, the perfluoroalkyl sulfanilic acid; The perfluoroalkyl ichthyodin; The perfluoroalkyl potassium sulfonate; The fluorinated alkyl carboxylate;

3) fluorinated alkyl sulfonate; With

4) its mixture.

18, a kind of Hairspray compositions by claim 1, its intermediate ion fluorine surfactant is the mixture of a kind of perfluoroalkyl sulfonate and fluorinated alkyl quaternary ammonium iodide.

19, a kind of Hairspray compositions according to claim 1, wherein existing liquid excipient be about 80%～about 99%, and be selected from C ₁～C ₈Alkanol, water, carbitol, acetone with and composition thereof.

20, a kind of Hairspray compositions according to claim 2, wherein ion exchange resin has the weight average molecular weight at least about 500000.

21, a kind of have the hair jelly product of aqueous sprayable Hairspray compositions and a spraying disperser instrument of a kind of loading and the described Hairspray compositions of spraying, described Hairspray compositions is to be contained in the described spraying disperser instrument, and the feature of wherein said Hairspray compositions comprises:

A) ion fluorine surfactant about 0.01%～about 2%(weight);

B) about 0.1%～about 15%(weight) contain the macromolecular resin of haircuting of silicone; And

C) a kind of water that contains, the liquid excipient of monohydric alcohol or its mixture.

22, a kind of hair jelly product by claim 21, wherein said resin has the weight average molecular weight at least about 70000.

23, a kind of hair jelly product by claim 22, wherein said resin has the weight average molecular weight at least about 100000.

24, a kind of hair jelly product by claim 23, wherein said resin has about weight average molecular weight of 100000～about 1000000.

25, a kind of hair jelly product by claim 24, wherein said resin has about weight average molecular weight of 125000～about 200000.

26, a kind of hair jelly product by claim 21, wherein said resin comprises about 2%～about 75%(weight) ion monomer and about 25%～about 98%(weight) non-ionic monomer, and wherein said resin contains the weight at least about 0.5%() siliceous one monomers.

27, a kind of hair jelly product according to claim 21, wherein said resin comprises acrylic acid, methacrylic acid, dimethylaminoethyl acrylate methyl base amino-ethyl ester, quaternised dimethylaminoethyl acrylate methyl base amino-ethyl ester, maleic acid, the half ester of maleic anhydride, butenoic acid, the itaconic acid, diallyl dimethyl ammonium chloride, vinylpyridine, vinyl imidazole, styrene sulfonate or its mixture.

28, a kind of hair jelly product according to claim 27, wherein said resin is to be selected from C ₁～C ₂₄The acrylate of alcohol, C ₁～C ₂₄The methacrylate of alcohol, styrene, polystyrene macromolecular, vinylacetate, vinyl chloride, the vinyl propionic ester, vinylidene chloride, α-Jia Jibenyixi, t-butylstyrene, butadiene, cyclohexadiene, ethylene, propylene, vinyltoluene, and composition thereof.

29, a kind of hair jelly product by claim 28, wherein said resin contain and have the monomeric silicone macromole that contains following chemical formula:

X（Y）nSi（R）3-mZm

Wherein X is-vinyl group; Y is-divalent linker; R is-hydrogen atom, hydroxyl, low alkyl group, aryl, alkaryl, alkyl amino or alkoxyl; Z is a kind of monovalence siloxane polymerization part that has at least about 500 number-average molecular weights, and n is 0 or 1; And m is 1～3 integer.

30, a kind of hair jelly product by claim 29, wherein said fluorine surfactant is a kind of perfluoroalkyl sulfonate or a kind of fluorinated alkyl quaternary amine chloride, or its mixture.

31, a kind of hair jelly product by claim 30 wherein saidly is used to load and the instrument of the described compositions of spraying is a kind of aerosol spray container.

32, a kind of hair jelly product by claim 31 also contains a kind of aerosol propellants that is placed in the described container.

33, a kind of hair jelly product by claim 31, wherein said aerosol spray container is a kind of pump automiser spray, wherein air is as a kind of propellant.

34, a kind of hair jelly product by claim 21 wherein saidly is used to load and the instrument of the described compositions of spraying is a kind of non-aerosol pump automiser spray.

35, a kind of low volatile organic solvent hair jelly product, comprise that a kind of Hairspray compositions and one are used to load and the spraying disperser instrument of the described Hairspray compositions of spraying, described Hairspray compositions is to be loaded in the described spraying disperser instrument, and wherein said Hairspray compositions is characterised in that and comprises:

A) ion fluorine surfactant about 0.01%～about 2%(weight);

B) resin of haircuting of ion about 0.1%～about 15%(weight); With

C) a kind of liquid excipient contains the water and about 30%～about 80% the monohydric alcohol of composition weight of composition weight 10%～about 70%.

36, a kind of hair jelly product by claim 35, wherein said compositions contains 1%～about 60% water of having an appointment.

37, a kind of hair jelly product by claim 36, wherein said compositions contain 13%～about 50% the water of having an appointment.

38, a kind of hair jelly product by claim 37, wherein said compositions contains 14%～about 50% water of having an appointment.

39, a kind of hair jelly product by claim 35, wherein said resin contains the 2%～about 75%(weight of having an appointment) ion monomer and about 25%～about 98%(weight) non-ionic monomer, and wherein said resin contains 0.5%(weight at least) siliceous one monomers.

40, a kind of hair jelly product by claim 35, wherein said resin is made up of organic monomer basically.

41, a kind of hair jelly product by claim 39, wherein said resin contains half ester, butenoic acid, itaconic acid, diallyl dimethyl ammonium oxide, vinylpyridine, vinyl imidazole, styrene sulfonate or its mixture of acrylic acid, methacrylic acid, dimethylaminoethyl acrylate methyl base amino-ethyl ester, quaternised dimethylaminoethyl acrylate methyl base amino-ethyl ester, maleic acid, maleic anhydride.

42, a kind of hair jelly product by claim 41, wherein said resin is selected from: C ₁～C ₂₄Acrylate, the C of alcohol ₁～C ₂₄The methacrylate of alcohol, styrene, polystyrene macromolecular, vinylacetate, vinyl chloride, vinyl propionic ester, vinylidene chloride, α-Jia Jibenyixi, t-butylstyrene, butadiene, cyclohexadiene, ethylene, propylene, vinyltoluene and composition thereof.

43, a kind of hair jelly product by claim 42, wherein said resin comprise have a following molecular formula contain the macromolecular monomer of silicone:

X（Y）nSi（R）3-mZm

Wherein X is a vinyl group, and Y is a bivalence linking base group, R is-and hydrogen, low alkyl, aryl or alkoxyl; Z is the monovalence siloxane polymerization part that has at least about 500 number-average molecular weight; N is 0 or 1 and m is 1～3 integer.

44, a kind of Hairspray compositions according to claim 1, also contain ionic strength modifier system at least about 0.01%, it is made up of monomer cation and the anionic mixture of monomer basically, and wherein said cation and anion are non-surface active and are to be partially soluble at least in the described liquid excipient.

45, a kind of Hairspray compositions according to claim 21, also contain ionic strength modifier system at least about 0.01%, it is made up of monomer anion and the anionic mixture of monomer basically, wherein said cation and anion are non-surface active, and are to be partially soluble at least in the described liquid excipient.

46, a kind of Hairspray compositions according to claim 41, also contain ionic strength modifier system at least about 0.01%, it is made up of monomer cation and the anionic mixture of monomer basically, wherein said cation and anion are non-surface active, and are to be partially soluble at least in the described liquid excipient.

47, a kind of hair jelly product by claim 35 wherein saidly is used for loading and the described compositions of spraying is a kind of aerosol spray container.

48, a kind of hair jelly product by claim 47 also contains a kind of aerosol propellants that is placed in the described container.

49, a kind of hair jelly product by claim 47, wherein said aerosol spray container is a kind of pump automiser spray, wherein air is as propellant.

50, a kind of hair jelly product by claim 35 wherein saidly is used for loading and the described compositions of spraying is a kind of non-aerosol pump automiser spray.

51, a kind of method that the benefit of haircuting is provided on sending out comprises that composition spray with the claim 1 of effective dose is to hair.

52, a kind of method that the benefit of haircuting is provided on sending out comprises that composition spray with the claim 7 of effective dose is to hair.

53, a kind of method that the benefit of haircuting is provided on sending out comprises that composition spray with the claim 11 of effective dose is to hair.

54, a kind of method that the benefit of haircuting is provided on sending out comprises that composition spray with the claim 21 of effective dose is to hair.

55, a kind of method that the benefit of haircuting is provided on sending out comprises that composition spray with the claim 35 of effective dose is to hair.